CN114345391B - Carbon nitride/graphene/manganese dioxide bifunctional catalyst and preparation method and application thereof - Google Patents
Carbon nitride/graphene/manganese dioxide bifunctional catalyst and preparation method and application thereof Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a carbon nitride/graphene/manganese dioxide bifunctional catalyst, and a preparation method and application thereof, wherein the preparation method comprises the following steps: step 1, calcining and acidifying a carbon nitride precursor to obtain protonated carbon nitride; step 2, preparing manganese dioxide, and then adopting a silane coupling agent to react to obtain aminated manganese dioxide; step 3, carrying out suction filtration on the graphene dispersion liquid and the amination manganese dioxide dispersion liquid, and carrying out hydrothermal reaction to obtain a graphene/manganese dioxide material; and carrying out suction filtration on the protonated carbon nitride dispersion liquid on the graphene layer, and carrying out reaction treatment to obtain the carbon nitride/graphene/manganese dioxide bifunctional catalyst. The catalyst is applied to the synergistic catalysis of ozone oxidation and photocatalysis for treating water and sewage, degrading and mineralizing organic pollutants, and improving the treatment efficiency of water and sewage.
Description
Technical Field
The invention relates to the technical field of catalysis and the technical field of water and sewage treatment, in particular to a carbon nitride/graphene/manganese dioxide dual-function catalyst and a preparation method and application thereof.
Background
The removal of organic matter is an important content of water and sewage treatment, and in particular, some novel organic pollutants (such as some pesticides and medicines) are of great interest in the field of water and sewage treatment. The advanced oxidation technology is popular in water and sewage treatment because of various types, strong adaptability and high efficiency, wherein the catalytic ozonation technology is applied to the advanced treatment of water and sewage because of mild conditions, strong oxidizing capability and almost no secondary pollution. The photocatalytic oxidation technology has the outstanding advantages of mild conditions, clean process, energy conservation, almost no secondary pollution and the like, and has great development potential. By the two water treatment technologies of the synergistic catalytic ozonation and the photocatalytic oxidation, the respective advantages of the catalytic ozonation technology and the photocatalytic oxidation technology can be reflected, and a strong synergistic effect can be generated.
For example, "use MgMnO" published in chemical engineering 3 As a dual-function catalyst for synchronous catalytic ozonation and photocatalysis, the antibiotic pollutant "(" Efficient mineralization of aqueous antibiotics by simultaneous catalytic ozonation and photocatalysis using MgMnO ") in water can be effectively mineralized 3 as a bifunctional catalyst, jiang et al, chemical Engineering Journal,2019,358:48-57 "). Therefore, the catalyst capable of catalyzing ozone oxidation and photo-oxidation simultaneously is synthesized and is a key of the technology of synergetic catalysis of ozone oxidation and photo-catalytic oxidation, so that the efficiency of degrading and removing organic pollutants in water and sewage is greatly improved.
To obtain the synergistic effect of catalytic ozonation and photocatalytic oxidation, a bifunctional catalyst is first designed and prepared. Manganese dioxide is an active component for catalyzing ozone oxidation, has stable structure and low toxicity, and is widely applied to occasions for catalyzing ozone oxidation to treat water and sewage, but has low catalysis efficiency. For example, the literature of the hazardous materials journal is modified with reduced graphene oxide like alpha-MnO 2 Structurally efficient catalytic ozonation of bisphenol A "(" Efficient catalytic ozonation of bisphenol-A over reduced graphene oxide modified sea urchin-like alpha-MnO) 2 archimedes, li et al Journal of Hazardous Materials,2015,294:201-208 ") consider manganese dioxide to be less catalytically effective in treating water and some organics in sewage and still require improved catalytic capabilities. Carbon nitride has great application potential in photocatalytic oxidation treatment of water and sewage as a metal-free photocatalyst with high conduction band, however, the application of carbon nitride is limited by the problems of low quantum yield, low conductivity and the like.
The carbon nitride and the manganese dioxide are combined to prepare the bifunctional catalyst with synergistic catalytic ozonation and photocatalytic oxidation effects, and meanwhile, the problems of low carbon nitride quantum yield and low conductivity are expected to be solved, so that the method becomes a research direction in the field of bifunctional catalysis.
Disclosure of Invention
Aiming at the problems that the catalytic efficiency of manganese dioxide is to be improved and the yield of carbon nitride quanta and the conductivity are low, the invention provides a carbon nitride/graphene/manganese dioxide dual-function catalyst which is formed by arranging a carbon nitride layer, a graphene layer and an amination manganese dioxide layer in sequence.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of a carbon nitride/graphene/manganese dioxide bifunctional catalyst comprises the following steps:
step 2, manganese acetate and inorganic base react under the action of disodium ethylenediamine tetraacetate and a catalyst to prepare manganese dioxide, and then the manganese dioxide reacts with a silane coupling agent in a solvent to obtain aminated manganese dioxide;
step 3, sequentially carrying out suction filtration on the graphene dispersion liquid and the amination manganese dioxide dispersion liquid on a filter membrane to obtain a solid A, placing the solid A in water for hydrothermal reaction, filtering a product, and drying to obtain a graphene/manganese dioxide material;
and 4, placing the graphene/manganese dioxide material on a filter membrane, enabling a graphene layer to face upwards, carrying out suction filtration on the protonated carbon nitride dispersion liquid on the filter membrane to obtain a solid B, placing the solid B in water for reaction, and filtering and drying a product to obtain the carbon nitride/graphene/manganese dioxide bifunctional catalyst.
The invention relates to a preparation method of a carbon nitride/graphene/manganese dioxide catalyst with a sandwich structure, wherein a graphene layer in the catalyst can mediate electron transfer between carbon nitride and manganese dioxide, so that not only is recombination of electron-hole pairs on the carbon nitride delayed, but also electron circulation of manganese oxide in the oxidation-reduction process is accelerated, and thus, photocatalytic oxidation efficiency and catalytic ozonation efficiency are improved. The invention has simple process, ingenious design, unique catalyst structure and adjustable size. The catalyst is applied to the synergistic catalytic ozonation and photocatalytic oxidation treatment of water and sewage, and organic pollutants are degraded and mineralized, so that the catalytic ozonation and photocatalytic oxidation reactions can be simultaneously and synergistically oxidized, and the treatment efficiency of water and sewage is improved.
In the step 1, the carbon nitride precursor comprises any one of urea, dicyandiamide, melamine and guanidine hydrochloride; the calcination temperature of the carbon nitride precursor is 500-600 ℃, the calcination time is 2-6h, and the heating speed is 2-3 ℃/min. The carbon nitride synthesized by different precursors has obvious difference in morphology and structure, thereby affecting the specific surface area; the temperature at which the precursor is calcined is different, and the crystallization degree of the obtained sample is different, so that the photoelectric property and the photocatalytic activity of the sample are affected; the precursor is continuously decomposed by prolonging the calcination time, the crystallization degree of the obtained carbon nitride is improved, the transmission path of carriers is shortened, electron hole pairs can be effectively separated, the utilization rate of the carriers is improved, but the long calcination time can lead to continuous growth of the carbon nitride crystal and change of a layered structure, reduce the surface area of the carbon nitride crystal and influence the photocatalytic performance.
Preferably, dicyandiamide is used as a precursor, and the carbon nitride powder is obtained by uniformly heating at a speed of 2.3 ℃/min and calcining at 550 ℃ for 4 hours.
In the step 1, inorganic acid and carbon nitride powder are mixed for acidification, and the aim is to change the surface charge of the carbon nitride material from negative to positive through protonation modification, so that the graphene nano-sheets with negative surface charge can be conveniently connected with the graphene nano-sheets through strong static self-assembly.
Preferably, the inorganic acid comprises any one of hydrochloric acid, sulfuric acid and nitric acid, the mass ratio of the carbon nitride to the inorganic acid is 0.01-0.1:1, and the stirring time is 0.5-1 h, so that the carbon nitride is fully acidified.
Preferably, the acidified carbon nitride is washed with water to neutrality to remove the mineral acid.
In the step 2, the mass ratio of the manganese acetate to the disodium edetate to the inorganic base to the catalyst is 0.5-2.5:0.5-2.5:2-5:1.
Preferably, the inorganic base comprises any one of sodium hydroxide, potassium hydroxide and lithium hydroxide; the catalyst comprises any one of sodium thiosulfate and/or sodium sulfite.
The reaction temperature for preparing manganese dioxide in the step 2 is 80-140 ℃ and the reaction time is 6-15h.
Preferably, the reaction temperature is 100 ℃, the reaction time is 12 hours, and the complete growth of manganese dioxide crystals is ensured.
Preferably, the silane coupling agent comprises any one of 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, and N- (2-aminoethyl) -3-aminopropyl trimethoxysilane; the mass ratio of the silane coupling agent to the manganese dioxide is 50-100:1.
The reaction temperature for preparing the amination manganese dioxide in the step 2 is 70-100 ℃ and the reaction time is 9-15h. The proper improvement of the hydrothermal reaction temperature and the extension of the reaction time are beneficial to the growth of manganese dioxide crystals, but the too high temperature and the too long reaction time can cause the thermodynamic instability of manganese dioxide, lead to appearance transformation and agglomeration phenomena and further influence the catalytic effect.
The solvent used for preparing the manganese dioxide and the aminated manganese dioxide in the step 2 comprises any one of water, toluene, methanol and ethanol.
In steps 3 and 4, the mass ratio of graphene, aminated manganese dioxide and carbon nitride is 0.5-1:0.8-1.2:0.8-1.2.
Wherein the graphene dispersion liquid is prepared by dissolving graphene in a solvent, and the mass ratio of the graphene to the solvent is 1 x 10 -4 ～1*10 -3 :1, a step of; preferably, the graphene dispersion is subjected to ultrasonic treatment and centrifugation after being dissolved, so that the graphene is fully dispersed in the solvent. The ultrasonic time is 1-4 hours; the rotational speed of the centrifugal process is 500-1000 rpm, and the centrifugal time is 30-60 min.
Preferably, the concentration of the carbon nitride dispersion is 0.5 to 2g/L. The concentration of the aminated manganese dioxide dispersion liquid is 0.5-2 g/L.
Preferably, the solvent used for the graphene dispersion, the carbon nitride dispersion, and the aminated manganese dioxide dispersion includes at least one of water, N-dimethylformamide, methanol, ethanol, toluene, acetone, tetrahydrofuran, and glycerin.
The hydrothermal reaction temperature of the solid A is 120-160 ℃, and the reaction time is 10-14h, graphene and aminated manganese dioxide are combined firstly, and amino groups on the surface of the manganese dioxide are covalently combined with unsaturated bonds on the surface of the graphene in the hydrothermal reaction process to form an aminated manganese dioxide/graphene double-layer structure compound.
The reaction temperature of the solid B is 60-80 ℃ and the reaction time is 2-6h. And then coating a carbon nitride material on the surface of the graphene layer of the solid A to form a sandwich structure of carbon nitride/graphene/manganese dioxide, and using the graphene layer as an intermediate of carbon nitride and manganese dioxide to mediate electron transfer between the carbon nitride and the manganese dioxide, so that the problems of low conductivity of the carbon nitride and easiness in recombination of photo-generated carriers are solved, and meanwhile, the electron circulation of manganese oxide in the oxidation-reduction process is accelerated.
The invention also provides the carbon nitride/graphene/manganese dioxide bifunctional catalyst prepared by the preparation method. The catalyst is applied to the synergistic catalytic ozonation and photocatalytic oxidation treatment of water and sewage, and organic pollutants are degraded and mineralized, so that the catalytic ozonation and photocatalytic oxidation reactions can be simultaneously and synergistically oxidized, and the treatment efficiency of water and sewage is improved.
The invention also provides application of the carbon nitride/graphene/manganese dioxide bifunctional catalyst in catalytic treatment of water and sewage, such as catalytic degradation of water and sewage containing any one of cefalexin, ciprofloxacin, 2, 4-dichlorophenoxyacetic acid and diuron. The catalyst can catalyze ozone oxidation and photooxidation simultaneously, and has remarkable effect of treating organic pollutants in water and sewage.
Compared with the prior art, the invention has the following beneficial effects:
(1) The sandwich structure carbon nitride/graphene/manganese dioxide bifunctional catalyst prepared by the invention utilizes the graphene layer as an intermediate layer of carbon nitride and manganese dioxide to mediate electron transfer between the carbon nitride and the manganese dioxide, so that the problem of low conductivity of the carbon nitride is solved, meanwhile, electron circulation of manganese oxide in the oxidation-reduction process is accelerated, the catalyst can catalyze ozone oxidation and photooxidation at the same time, and the catalytic effect is obviously improved.
(2) The catalyst disclosed by the invention is ingenious in design, unique in catalyst structure and adjustable in size of each layer of material, and can be adjusted according to actual conditions for treating pollutants needing more ozone oxidation or pollutants needing more photocatalysis according to different application scenes.
(3) The preparation method of the catalyst has simple process, does not need complex reaction equipment, can realize large-scale production, and is suitable for industrialization.
Drawings
Fig. 1 is an SEM image of graphene prepared in example 1 at 1000 x magnification.
FIG. 2 is an SEM image of 10000 times of carbon nitride prepared from different precursors of example 2, where (a), (b), (C), and (d) are g-C, respectively 3 N 4 -1、g-C 3 N 4 -2、g-C 3 N 4 -3、g-C 3 N 4 -4。
FIG. 3 is a graph showing the degradation of cefalexin in water by carbon nitride photocatalytic treatment prepared from different precursors in example 2.
FIG. 4 is a graph showing the degradation of cefalexin in water by carbon nitride photocatalytic treatment prepared at different calcination temperatures in example 3.
Figure 5 is an XRD pattern of carbon nitride prepared at different calcination temperatures for example 3.
FIG. 6 is a graph showing the degradation of cefalexin in water by carbon nitride photocatalytic treatment prepared in example 4 at different calcination times.
Fig. 7 is an SEM image of 10000 times of the protonated carbon nitride prepared in example 5.
FIG. 8 is a graph showing the degradation of cephalexin in manganese dioxide catalyzed ozonation treated water prepared at different hydrothermal reaction temperatures of example 6.
FIG. 9 is an SEM image of manganese dioxide prepared at various hydrothermal reaction temperatures of example 6 at 10000 times, and (a), (b), (c), and (d) are the results at temperatures of 80℃at 100℃at 120℃and 140℃respectively.
FIG. 10 is a graph showing the degradation of cephalexin in manganese dioxide catalyzed ozonation treated water prepared by various hydrothermal reaction times of example 7.
FIG. 11 is an SEM image of manganese dioxide obtained in example 7 at 10000 times magnification, wherein (a), (b), (c) and (d) are respectively hydrothermal reaction times of 6h, 9h, 12h and 15h.
FIG. 12 is an SEM image of the aminated manganese dioxide prepared in example 8 at 10000 Xmagnification.
Fig. 13 is an SEM image of the sandwich carbon nitride/graphene/manganese dioxide catalyst prepared in example 9 at 1000 x magnification.
Fig. 14 is an SEM image of the catalyst of comparative example 1 having a carbon nitride/graphene double-layer structure at 10000 x magnification.
Fig. 15 is an SEM image of the manganese dioxide/graphene double-layer structure catalyst of comparative example 2 at 10000 x magnification.
FIG. 16 is a graph showing degradation of cefalexin in application example 1 and application comparative examples 1 to 3.
Fig. 17 is a degradation graph of ciprofloxacin of application example 2.
FIG. 18 is a degradation graph of 2, 4-dichlorophenoxyacetic acid (2, 4-D) of application example 3.
Fig. 19 is a diuron degradation graph of application example 4.
FIG. 20 is a graph showing the COD removal rate of the phenol solution of application example 5.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. Modifications and equivalents will occur to those skilled in the art upon understanding the present teachings without departing from the spirit and scope of the present teachings.
The raw materials adopted in the following specific embodiments are all purchased in the market, and are directly used without treatment.
Example 1
The preparation of the graphene dispersion liquid comprises the following specific processes:
100mg of graphene powder is added into 200mL of N, N-dimethylformamide, and after ultrasonic dispersion is carried out for 4 hours, the graphene powder is centrifuged at 850rpm for 45 minutes to obtain graphene dispersion liquid for standby.
And (3) drying the graphene dispersion liquid, and carrying out SEM scanning on the prepared graphene sample to observe the microscopic morphology of the graphene sample, wherein the result is shown in figure 1, the graphene is uniformly dispersed, no agglomeration phenomenon exists, and the thickness is 10-50nm.
Example 2
Urea, dicyandiamide, melamine and guanidine hydrochloride are heated from room temperature to 550 ℃ for 4 hours at a fixed heating rate of 2.3 ℃/min, and are respectively named as g-C 3 N 4 -1、g-C 3 N 4 -2、g-C 3 N 4 -3、g-C 3 N 4 -4. The microscopic morphology was observed by SEM scanning, and the results are shown in fig. 2. g-C synthesized by the four precursors 3 N 4 All show lamellar stacked graphite-like structures, but specific shapes are obviously different.
As shown in FIG. 2 (a), g-C synthesized by taking urea as a precursor is affected by ammonia released by pyrolysis of urea 3 N 4 -1 is formed by stacking relatively fluffy particles, which have a rough surface and a large distance. As shown in FIG. 2 (b), g-C synthesized from dicyandiamide as a precursor 3 N 4 -2 surface roughness, accompanied by a large number of small pieces of lamellar structure; and g-C synthesized by using melamine and guanidine hydrochloride as precursors 3 N 4 -3、g-C 3 N 4 The surface of-4 is smoother and consists essentially of a larger block structure, which indicates that the two precursors are susceptible to agglomeration during high temperature firing (as shown in fig. 2 (c) and (d)). g-C synthesized from dicyandiamide 3 N 4 Has rough surface morphology and larger specific surface area.
The catalyst is used for degrading cefalexin by photocatalytic oxidation, and the catalyst reaches adsorption balance before illumination, and the specific catalytic process is as follows:
200mL of water and 1mL of cefalexin with the concentration of 0.2g/L are added into the reactor, and the mixture is stirred and mixed uniformly by magnetic force. 5mg of the obtained carbon nitride was added to the solution, and an ultraviolet lamp (wavelength 254nm, power 15W) was turned on, and the instant was recorded as reaction time 0. About 2ml were sampled from the reactor at times 0min, 10s, 1min, 2min, 3min,4min and 5min, respectively. And (3) treating the water sample by a microporous filter membrane with the specification of 0.22 mu m, and measuring the concentration of the cefalexin by adopting a high performance liquid chromatograph.
The degradation effect of the cefalexin is shown in figure 3, and the photocatalytic performance of the carbon nitride prepared by different precursors is obviously different. After 5min of photocatalytic reaction, the removal rate of the carbon nitride prepared by taking urea, dicyandiamide, melamine and guanidine hydrochloride as precursors to cephalexin reaches 13.5%, 14.9%, 6.7% and 10.4% respectively. The carbon nitride prepared by taking dicyandiamide as a precursor has the best photocatalysis effect, and the concentration of the cefalexin can be reduced from 1.0mg/L to 0.85mg/L through a reaction for 5 min.
Example 3
Dicyandiamide is calcined for 4 hours at different calcining temperatures (500 ℃, 525 ℃, 550 ℃, 575 ℃ and 600 ℃) respectively to obtain a carbon nitride catalyst, the obtained catalyst is used for photocatalytic oxidation degradation of cephalexin, the catalytic process is the same as in example 2, the catalyst reaches adsorption balance before illumination, and the degradation effect of cephalexin is shown in figure 4. After 5min of photocatalytic reaction, the degradation rates of the carbon nitride prepared at different calcination temperatures on cephalexin are 13.9%, 14.4%, 14.9%, 12.6% and 11.7%, respectively, which means that 550 ℃ is the most suitable calcination temperature. If the calcination temperature is kept below 550 ℃, the precursor may not be completely decomposed, resulting in a part of the sample being covered by the precursor, a smaller surface area, and a lower degree of crystallization; and when the calcination temperature is higher than 550 ℃, decomposition and sintering of carbon nitride at high temperature may be caused, thereby affecting photocatalytic performance thereof.
The XRD patterns of carbon nitride samples calcined at different temperatures are shown in FIG. 5. The XRD patterns of the five samples each exhibited two distinct characteristic diffraction peaks at about 13.2 ° and 27.4 °, belonging to the (100) and (002) planes of carbon nitride, respectively, corresponding to the interlayer stack and in-plane structure packing of the aromatic segments at a distance of 0.33 nm. The peak width of the sample obtained by calcining at 550 ℃ is the sharpest, the half-peak width is the smallest, which indicates that the crystallization degree is the highest, the characteristic peak intensity is large, the photocatalytic reaction is more facilitated, and the result is consistent with the experimental result of photocatalytic oxidation of cephalexin of the sample.
Example 4
Dicyandiamide is calcined at 550 ℃ for different time (2 h, 3h, 4h, 5h and 6 h) to obtain carbon nitride catalyst, the obtained catalyst is used for photocatalytic oxidation degradation of cephalexin, the catalytic process is the same as that of example 2, the catalyst reaches adsorption equilibrium before illumination, and the degradation effect of cephalexin is shown in figure 6.
With the extension of the calcination time, the photocatalytic oxidative degradation capability of the carbon nitride to the cefalexin tends to be increased and then decreased. When the calcination time is increased from 2h to 4h, the removal rate of the cefalexin is improved from 13.1% to 13.6% to 15.1%. And the calcination time is prolonged continuously, the photocatalytic oxidative degradation capability of the carbon nitride to the cefalexin is reduced, and the removal rate of 14.4% of the sample obtained from the calcination time of 5 hours is reduced to 9.5% of the sample obtained from the calcination time of 6 hours. The calcination time is prolonged to continuously decompose the precursor, the crystallization degree of the carbon nitride is improved, the transmission path of the carrier is shortened, and the electron hole pair can be effectively separated, so that the utilization rate of the carrier is improved. However, further increase of the calcination time causes continuous growth of the carbon nitride crystal and change of the layered structure, which reduces the surface area and adversely affects the photocatalytic performance. Thus, optimized dicyandiamide preparation of g-C 3 N 4 The calcination time of (2) was 4h.
Example 5
The preparation of the protonated carbon nitride comprises the following specific processes:
weighing 10g of dicyandiamide, putting the dicyandiamide into a muffle furnace, heating to 600 ℃ at 2.3 ℃/min, calcining for 2 hours, and naturally cooling to obtain carbon nitride powder. 1g of carbon nitride powder was weighed, added to 25mL of concentrated hydrochloric acid with a concentration of 10mol/L, magnetically stirred for 1h, and repeatedly washed until the pH was neutral. Placing the product in an oven at 80 ℃ for drying for 12 hours, and taking 50mg of solid to put into 100mL of water for ultrasonic treatment for 2 hours to obtain a protonated carbon nitride dispersion liquid; the obtained protonated carbon nitride powder after drying is subjected to SEM scanning, the morphology is shown in figure 7, and the particle size of the protonated carbon nitride particles is basically below 500nm, and has a rough surface.
Example 6
0.5g of manganese acetate and 1.5g of disodium edetate were dissolved in 50mL of water under magnetic stirring. Subsequently, 50mL of a 0.25mol/L aqueous sodium hydroxide solution was added dropwise to the above solution. Then, 50mL of a 0.12mol/L aqueous solution of sodium thiosulfate was added dropwise to the above solution. Fixing the mixed solution for 9h in a hydrothermal reaction time, synthesizing manganese dioxide at different hydrothermal reaction temperatures (80 ℃, 100 ℃, 120 ℃ and 140 ℃), filtering the obtained precipitate, washing the precipitate with water for a plurality of times, and drying the precipitate for 12h at 80 ℃ to obtain ultrathin manganese dioxide nano-sheets; the obtained manganese dioxide is used for catalyzing the oxidative degradation of cefalexin by ozone, and the result is shown in figure 8. The catalytic process comprises the following steps:
before the reaction, the ozone generator is started to produce ozone for 30min for preheating, so that the flow of the oxygen/ozone mixed gas is ensured to be 0.1L/min. 200mL of water and 1mL of cefalexin with the concentration of 0.2g/L are added into the reactor, and the mixture is stirred and mixed uniformly by magnetic force. 5mg of the obtained manganese dioxide was added to the solution, and an ultraviolet lamp (wavelength 254nm, power 15W) was turned on and ozone was introduced, and the instant was recorded as reaction time 0. About 2ml were sampled from the reactor at times 0min, 10s, 1min, 1.5min, 2min, 2.5min, 3min, 3.5min, 4min, 4.5min and 5min, respectively. And (3) treating the water sample by a microporous filter membrane with the specification of 0.22 mu m, and measuring the concentration of the cefalexin by adopting a high performance liquid chromatograph.
After 5min of catalytic reaction, the removal rates of the manganese dioxide catalyst synthesized by hydrothermal reaction at 80 ℃, 100 ℃, 120 ℃ and 140 ℃ on the cefalexin in water respectively reach 87.9%, 95.2%, 83.2% and 66.1%. The hydrothermal temperature of the manganese dioxide catalyst synthesized from low to high shows the tendency of rising and then falling on the degradation efficiency of the cefalexin, wherein the manganese dioxide catalyst synthesized by hydrothermal method has the optimal catalytic activity at 100 ℃. This may be due to the fact that the hydrothermal reaction temperature is properly increased to facilitate the growth of manganese dioxide crystals, but the manganese dioxide is thermodynamically unstable due to the excessive temperature, and the crystal phase is changed, and the catalytic activity of the synthesized manganese dioxide at 100 ℃ is obviously higher than that of other samples, which indicates that 100 ℃ is the most suitable hydrothermal reaction temperature.
The obtained manganese dioxide powder was subjected to SEM scanning, and the morphology is shown in FIG. 9, and the results of (a), (b), (c) and (d) are the results of hydrothermal reaction at 80 ℃, 100 ℃, 120 ℃ and 140 ℃, respectively. The manganese dioxide sheet layer prepared at the hydrothermal temperature of 80 ℃ is loose, but the nano sheet is smaller, which indicates that the crystal does not grow completely. When the hydrothermal temperature is raised to 100 ℃, the length of the manganese dioxide sheet layer is further increased to about 1 mu m, and the appearance is more plump. When the hydrothermal reaction temperature is 120 ℃, obvious agglomeration phenomenon appears in the synthesized manganese dioxide, and the surface of the synthesized manganese dioxide tends to be smooth from irregular sheets. When the hydrothermal reaction temperature is increased to 140 ℃, the synthesized manganese dioxide is transformed into crystal form, and the manganese dioxide with a rod-shaped structure and petal-shaped manganese dioxide are mutually attached. This is probably because the increase in temperature increases the reaction rate, accelerates the process of "nucleation-dissolution-anisotropic growth-crystallization", resulting in the formation of nanorod-shaped manganese dioxide. Comparison of SEM images of samples prepared by different hydrothermal temperature reactions further proves that 100 ℃ is favorable for synthesizing manganese dioxide with complete morphology, larger surface area and higher crystallization degree by taking the sample as the hydrothermal reaction temperature.
Example 7
According to example 6, manganese acetate is used as a precursor, the fixed hydrothermal temperature is 100 ℃, the catalytic ozonation capacity of manganese dioxide prepared under different hydrothermal reaction time (6 h, 9h, 12h and 15 h) on cefalexin in water is studied, and the catalytic process is the same as in example 6, and the result is shown in fig. 10.
As the hydrothermal reaction time is increased from 6h to 9h, the removal rate of the prepared manganese dioxide catalyst for catalyzing the ozonation of cephalexin in 5min is increased from 91.9% to 95.2%. And the hydrothermal time is continuously increased to 12h and 15h, and the removal rate of the prepared manganese dioxide catalyst to the cephalexin is reduced to 87.6% and 77.1% in the catalytic ozonation reaction for 5 min.
The obtained manganese dioxide powder was subjected to SEM scanning, and the morphology of the manganese dioxide powder was shown in fig. 11, wherein (a), (b), (c) and (d) were hydrothermal reaction times of 6h, 9h, 12h and 15h, respectively. And when the hydrothermal reaction time is 6 hours, the synthesized manganese dioxide nano-sheet is smaller, and the crystal growth is incomplete. When the hydrothermal reaction time is 9h, the synthesized manganese dioxide nano-sheet has a larger petal shape, which indicates that the crystal growth is complete. When the hydrothermal time is prolonged to 12 hours, the structure of manganese dioxide is collapsed and agglomerated, and petal-shaped structure parts are crushed and converted into particles. When the hydrothermal time is prolonged to 15 hours, the agglomeration among manganese dioxide crystals is more obvious, and the loose petal-shaped structures almost disappear and are converted into irregular particles. Thus, the manganese dioxide synthesized at a hydrothermal reaction time of 9 hours is more suitable for catalyzing ozone oxidation.
Example 8
This example is a preparation of aminated manganese dioxide, and comprises the following specific procedures:
0.5g of manganese acetate and 1.5g of disodium edetate were dissolved in 50mL of water under magnetic stirring. Subsequently, 50mL of a 0.25mol/L aqueous sodium hydroxide solution was added dropwise to the above solution. Then, 50mL of a 0.12mol/L aqueous solution of sodium thiosulfate was added dropwise to the above solution. Maintaining the mixed solution at 40 ℃ for 12 hours, filtering the obtained precipitate, washing with water for several times, and drying at 80 ℃ for 12 hours to obtain ultrathin manganese dioxide nano-sheets;
100mg of the obtained manganese dioxide was poured into 25mL of toluene, and 0.5mL of 3-aminopropyl triethoxysilane was added dropwise under magnetic stirring, followed by heating to 80℃and magnetic stirring for reflux for 12 hours. Repeatedly washing the product with ethanol and water until the pH value is neutral, and drying the product in an oven at 80 ℃ to obtain the aminated manganese dioxide. Adding 50mg of the obtained aminated manganese dioxide into 50mL of water, and magnetically stirring to obtain an aminated manganese dioxide dispersion liquid; the obtained aminated manganese dioxide after drying the dispersion liquid is subjected to SEM scanning, and the result is shown in figure 12, wherein the ultrathin manganese dioxide nanosheets are formed into petal shapes with the diameter of 5-10 mu m.
Example 9
The embodiment is a preparation method of a carbon nitride/graphene/manganese dioxide bifunctional catalyst with a sandwich structure, and the specific process is as follows:
2mL of the aminated manganese dioxide dispersion prepared in example 8 was vacuum filtered on a filter, and then 1mL of the graphene dispersion prepared in example 1 was vacuum filtered on the filter and the whole solid piece on the filter was scraped off. Adding the solid and 190mL of water into a reaction kettle, performing hydrothermal reaction for 12 hours at 140 ℃, filtering and drying the obtained product to obtain a graphene/manganese dioxide material;
placing the obtained graphene/manganese dioxide on a filter membrane, enabling a graphene layer to face upwards, enabling a manganese dioxide layer to face the filter membrane, filtering 10mL of water on the filter membrane, wetting the graphene/manganese dioxide, then vacuum-filtering 3mL of the protonated carbon nitride dispersion liquid prepared in the example 5 on the filter membrane, scraping the obtained material from the filter membrane, adding the materials into the water, magnetically stirring and heating the materials to 75 ℃ for condensation reflux for 4 hours, filtering and drying the obtained product, and obtaining the carbon nitride/graphene/manganese dioxide sandwich catalyst, wherein the microstructure is shown in fig. 13, the prepared sandwich catalyst is of a uniform three-layer structure, and the thickness of each layer is 5-10 mu m.
Comparative example 1
The comparative example is the preparation of a catalyst with a carbon nitride/graphene double-layer structure, and the specific process is as follows:
3mL of the protonated carbon nitride dispersion prepared in example 5 was vacuum filtered on a filter, and then 2mL of the graphene dispersion prepared in example 1 was vacuum filtered on the filter. Scraping the obtained material from the filter membrane, adding the material into water, magnetically stirring and heating to 75 ℃ for condensation reflux for 4 hours, filtering and drying the obtained product to obtain the carbon nitride/graphene double-layer structure catalyst, wherein as shown in fig. 14, the carbon nitride and graphene are combined more tightly, and the hierarchy is distinct.
Comparative example 2
The preparation method of the catalyst with the manganese dioxide/graphene double-layer structure in the comparative example comprises the following specific processes: 3mL of the aminated manganese dioxide dispersion prepared in example 8 was vacuum filtered on a filter, and then 2mL of the graphene dispersion prepared in example 1 was vacuum filtered on the filter and the whole solid piece on the filter was scraped off. The solid and 190mL of water are added into a reaction kettle together, hydrothermal reaction is carried out for 12 hours at 140 ℃, the obtained product is filtered and dried, and the manganese dioxide/graphene double-layer structure catalyst is obtained, as shown in figure 15, the manganese dioxide maintains the original petal-shaped structure and is tightly attached to graphene.
Application example 1
The embodiment is a sandwich structure carbon nitride/graphene/manganese dioxide catalyst for catalytic oxidation of cefalexin in water, and the process is as follows:
before the reaction, the ozone generator is started to produce ozone for 30min for preheating, so that the flow of the oxygen/ozone mixed gas is ensured to be 0.1L/min. 200mL of water and 1mL of cefalexin with the concentration of 0.2g/L are added into the reactor, and the mixture is stirred and mixed uniformly by magnetic force. 5mg of the catalyst with the sandwich structure prepared in example 9 was added to the solution, and simultaneously an ultraviolet lamp (wavelength 254nm, power 15W) was turned on and ozone was introduced, and this instant was recorded as the reaction 0 time. About 2ml were sampled from the reactor at times 0min, 10s, 1min, 1.5min, 2min, 2.5min, 3min, 3.5min, 4min, 4.5min and 5min, respectively. After a water sample is treated by a microporous filter membrane with the specification of 0.22 mu m, measuring the concentration of the cefalexin by adopting a high performance liquid chromatograph, and the result is shown in figure 16, wherein the carbon nitride/graphene/manganese dioxide catalyst with a sandwich structure can catalyze and degrade almost 100% of the cefalexin within 3min, namely, the concentration is lower than the detection limit of 1 mu g/L.
Comparative example 1 was used
200mL of water and 1mL of cefalexin with the concentration of 0.2g/L are added into the reactor, and the mixture is stirred and mixed uniformly by magnetic force. To the solution, 5mg of the protonated carbon nitride obtained in example 5 was added, and simultaneously an ultraviolet lamp (wavelength 254nm, power 15W) was turned on, and this moment was recorded as reaction time 0. About 2ml were sampled from the reactor at times 0min, 10s, 1min, 2min, 3min,4min and 5min, respectively. After the water sample is treated by a microporous filter membrane with the specification of 0.22 mu m, the concentration of the cefalexin is measured by a high performance liquid chromatograph, and the result is shown in figure 16, and 11.5% of the cefalexin is removed after the reaction is carried out for 5 min.
Comparative example 2 was used
Before the reaction, the ozone generator is started to produce ozone for 30min for preheating, so that the flow of the oxygen/ozone mixed gas is ensured to be 0.1L/min. 200mL of water and 1mL of cefalexin with the concentration of 0.2g/L are added into the reactor, and the mixture is stirred and mixed uniformly by magnetic force. To the solution, 5mg of the aminated manganese dioxide prepared in example 8 was added, and ozone was introduced, and the instant was recorded as reaction time 0. About 2ml were sampled from the reactor at times 0min, 10s, 1min, 2min, 3min,4min and 5min, respectively. After the water sample is treated by a microporous filter membrane with the specification of 0.22 mu m, the concentration of the cefalexin is measured by a high performance liquid chromatograph, the result is shown in figure 16, and 25.6% of the cefalexin is removed after the reaction is carried out for 5 min.
Comparative example 3 was used
Before the reaction, the ozone generator is started to produce ozone for 30min for preheating, so that the flow of the oxygen/ozone mixed gas is ensured to be 0.1L/min. 200mL of water and 1mL of cefalexin with the concentration of 0.2g/L are added into the reactor, and the mixture is stirred and mixed uniformly by magnetic force. To the solution, 1ml of the graphene dispersion prepared in example 1, 2mg of the protonated carbon nitride prepared in example 2, and 2mg of the aminated manganese dioxide prepared in example 3 were added, respectively, and an ultraviolet lamp (wavelength 254nm, power 15W) was turned on and ozone was introduced, and this moment was recorded as reaction time 0. About 2ml were sampled from the reactor at times 0min, 10s, 1min, 2min, 3min,4min and 5min, respectively. After the water sample is treated by a microporous filter membrane with the specification of 0.22 mu m, the concentration of the cefalexin is measured by a high performance liquid chromatograph, the result is shown in figure 16, and 25.9% of the cefalexin is removed after the reaction is carried out for 5 min.
As can be seen from application examples 1 and application comparative examples 1-3, the carbon nitride/graphene/manganese dioxide sandwich structure catalyst prepared by the method has excellent catalytic effects compared with single photocatalysis or catalytic ozonation, and compared with a mixture of carbon nitride, graphene and manganese dioxide for simultaneously catalyzing ozonation and photocatalytic oxidation, and has great difference, and the catalytic effect of the carbon nitride/graphene/manganese dioxide sandwich structure catalyst is remarkably improved.
Application example 2
The embodiment is an application of a carbon nitride/graphene/manganese dioxide bifunctional catalyst with a sandwich structure in catalyzing and degrading ciprofloxacin in water treatment, and the process is as follows:
before the reaction, the ozone generator is started to produce ozone for 30min for preheating, so that the flow of the oxygen/ozone mixed gas is ensured to be 0.1L/min. 200mL of water and 1mL of ciprofloxacin solution with the concentration of 0.2g/L are added into the reactor, and the mixture is stirred and mixed evenly by magnetic force. 5mg of the catalyst with the sandwich structure prepared in example 9 was added to the solution, and simultaneously an ultraviolet lamp (wavelength 254nm, power 15W) was turned on and ozone was introduced, and this instant was recorded as the reaction 0 time. About 2ml were sampled from the reactor at times 0min, 10s, 1min, 1.5min, 2min, 2.5min, 3min, 3.5min, 4min, 4.5min and 5min, respectively. After the water sample is treated by a microporous filter membrane with the specification of 0.22 mu m, the concentration of ciprofloxacin is measured by a high performance liquid chromatograph, and the result is shown in figure 17, 98.8% of ciprofloxacin is removed after 2 minutes of reaction, and almost completely removed after 2.5 minutes of reaction.
Application example 3
The embodiment is an application of a carbon nitride/graphene/manganese dioxide bifunctional catalyst with a sandwich structure in catalytic degradation of 2, 4-dichlorophenoxyacetic acid (2, 4-D) in sewage treatment, and the process is as follows:
before the reaction, the ozone generator is started to produce ozone for 30min for preheating, so that the flow of the oxygen/ozone mixed gas is ensured to be 0.1L/min. 200mL of water and 1mL of 2, 4-dichlorophenoxyacetic acid (2, 4-D) solution with the concentration of 0.2g/L are added into the reactor, and the mixture is stirred and mixed uniformly by magnetic force. 5mg of the catalyst with the sandwich structure prepared in example 9 was added to the solution, and simultaneously an ultraviolet lamp (wavelength 254nm, power 15W) was turned on and ozone was introduced, and this instant was recorded as the reaction 0 time. About 2ml were sampled from the reactor at times 0min, 10s, 1min, 1.5min, 2min, 2.5min, 3min, 3.5min, 4min, 4.5min and 5min, respectively. After the water sample is treated by a microporous filter membrane with the specification of 0.22 mu m, the concentration of 2, 4-dichlorophenoxyacetic acid (2, 4-D) is measured by a high performance liquid chromatograph, and the result is shown in figure 18, 88.7% of 2,4-D is removed after 3 minutes of reaction, and 2,4-D is almost completely removed after 4 minutes of reaction.
Application example 4
The embodiment is an application of a carbon nitride/graphene/manganese dioxide bifunctional catalyst with a sandwich structure in catalytic degradation of diuron in water treatment, and the process is as follows:
before the reaction, the ozone generator is started to produce ozone for 30min for preheating, so that the flow of the oxygen/ozone mixed gas is ensured to be 0.1L/min. 200mL of water and 1mL of diuron solution with the concentration of 0.2g/L are added into the reactor, and the mixture is stirred and mixed uniformly by magnetic force. 5mg of the catalyst with the sandwich structure prepared in example 9 was added to the solution, and simultaneously an ultraviolet lamp (wavelength 254nm, power 15W) was turned on and ozone was introduced, and this instant was recorded as the reaction 0 time. About 2ml were sampled from the reactor at times 0min, 10s, 1min, 1.5min, 2min, 2.5min, 3min, 3.5min, 4min, 4.5min and 5min, respectively. After the water sample is treated by a microporous filter membrane with the specification of 0.22 mu m, the diuron concentration is measured by a high performance liquid chromatograph, the result is shown in figure 19, and 99.1% of diuron is removed after 4 minutes of reaction.
Application example 5
The embodiment is an application of a carbon nitride/graphene/manganese dioxide bifunctional catalyst with a sandwich structure in catalytic degradation of phenol Chemical Oxygen Demand (COD) in water treatment, and the process is as follows:
before the reaction, the ozone generator is started to produce ozone for 30min for preheating, so that the flow of the oxygen/ozone mixed gas is ensured to be 0.1L/min. 190mL of water and 10mL of phenol solution with a concentration of 4g/L are added into the reactor, and the mixture is stirred and mixed uniformly by magnetic force, so that the initial concentration of phenol is 200mg/L. 5mg of the catalyst with the sandwich structure prepared in example 9 was added to the solution, and simultaneously an ultraviolet lamp (wavelength 254nm, power 15W) was turned on and ozone was introduced, and this instant was recorded as the reaction 0 time. About 2ml were sampled from the reactor at times 0min, 10s, 1min, 1.5min, 2min, 2.5min, 3min, 3.5min, 4min, 4.5min and 5min, respectively. After the water sample is treated by a microporous filter membrane with the specification of 0.22 mu m, the COD of the solution is measured by a high performance liquid chromatograph, and the result is shown in figure 20, and for 200mg/L of phenol solution, 84.2% of the COD is removed after 5 minutes of reaction.
Claims (8)
1. A preparation method of a carbon nitride/graphene/manganese dioxide bifunctional catalyst comprises the following steps:
step 1, calcining and acidifying a carbon nitride precursor to obtain protonated carbon nitride; the acidification is carried out by mixing inorganic acid with carbon nitride powder, the mass ratio of the carbon nitride to the inorganic acid is 0.01-0.1:1, and the stirring time is 0.5-1 h;
step 2, manganese acetate and inorganic base react under the action of disodium ethylenediamine tetraacetate and a catalyst to prepare manganese dioxide, and then the manganese dioxide reacts with a silane coupling agent in a solvent to obtain aminated manganese dioxide;
step 3, sequentially carrying out suction filtration on the graphene dispersion liquid and the amination manganese dioxide dispersion liquid on a filter membrane to obtain a solid A, placing the solid A in water for hydrothermal reaction, filtering a product, and drying to obtain a graphene/manganese dioxide material;
step 4, placing the graphene/manganese dioxide material on a filter membrane, enabling a graphene layer to face upwards, carrying out suction filtration on the protonated carbon nitride dispersion liquid on the filter membrane to obtain a solid B, placing the solid B in water for reaction, and filtering and drying a product to obtain the carbon nitride/graphene/manganese dioxide bifunctional catalyst;
the reaction temperature for preparing manganese dioxide in the step 2 is 80-140 ℃ and the reaction time is 6-15h;
the mass ratio of the graphene to the aminated manganese dioxide to the carbon nitride is 0.5-1:0.8-1.2:0.8-1.2;
the reaction temperature of the solid B is 60-80 ℃ and the reaction time is 2-6h;
the reaction temperature for preparing the amination manganese dioxide in the step 2 is 70-100 ℃ and the reaction time is 9-15h.
2. The method for preparing the carbon nitride/graphene/manganese dioxide dual-function catalyst according to claim 1, wherein in the step 1, the carbon nitride precursor comprises any one of urea, dicyandiamide, melamine and guanidine hydrochloride; the calcination temperature of the carbon nitride precursor is 500-600 ℃, the calcination time is 2-6h, and the heating speed is 2-3 ℃/min.
3. The method for preparing the carbon nitride/graphene/manganese dioxide bifunctional catalyst according to claim 1, wherein in the step 2, the mass of manganese acetate is 0.5g, the mass of disodium ethylenediamine tetraacetate is 1.5g, the mass of inorganic base is 0.5g of sodium hydroxide, and the mass of the catalyst is 0.949g of sodium thiosulfate.
4. The method for preparing the carbon nitride/graphene/manganese dioxide bifunctional catalyst according to claim 1, wherein the silane coupling agent comprises any one of 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, and N- (2-aminoethyl) -3-aminopropyl trimethoxysilane; the mass ratio of the silane coupling agent to the manganese dioxide is 50-100:1.
5. The method for preparing the carbon nitride/graphene/manganese dioxide bifunctional catalyst according to claim 1, wherein the hydrothermal reaction temperature of the solid A is 120-160 ℃ and the reaction time is 10-14h.
6. The method for preparing the carbon nitride/graphene/manganese dioxide bifunctional catalyst according to claim 1, wherein the solvent used for the graphene dispersion, the protonated carbon nitride dispersion and the aminated manganese dioxide dispersion comprises at least one of water, N-dimethylformamide, methanol, ethanol, toluene, acetone, tetrahydrofuran and glycerin.
7. The carbon nitride/graphene/manganese dioxide bifunctional catalyst prepared by the preparation method according to any one of claims 1 to 6.
8. The use of a carbon nitride/graphene/manganese dioxide bifunctional catalyst according to claim 7 for the catalytic treatment of water and sewage.
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